CN102185000A - Cadmium sulfide thin film solar cell and preparation method thereof - Google Patents

Cadmium sulfide thin film solar cell and preparation method thereof Download PDF

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CN102185000A
CN102185000A CN2011100844603A CN201110084460A CN102185000A CN 102185000 A CN102185000 A CN 102185000A CN 2011100844603 A CN2011100844603 A CN 2011100844603A CN 201110084460 A CN201110084460 A CN 201110084460A CN 102185000 A CN102185000 A CN 102185000A
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solar cell
sno
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李卫
冯良桓
张静全
武莉莉
蔡亚平
谢晗科
朱喆
高静静
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Sichuan University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E10/00—Energy generation through renewable energy sources
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    • Y02E10/547—Monocrystalline silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention belongs to the field of novel energy source materials and devices, in particular relates to a preparation method of a semiconductor film solar cell and provides a CdS homojunction solar cell structure, wherein Cd2SnO4 serves as a transparent conducting layer, n type CdS serves as a window layer, Zn2SnO4 serves as a buffering layer material between the transparent conducting layer and the window layer, and p type CdS serves as an absorbing layer. On the basis of the CdS homojunction solar cell structure, a CdS solar cell is prepared by a dry process. Namely, the preparation method comprises the following steps of: performing radio-frequency sputtering on the borosilicate or aluminosilicate glass to form the transparent conducting layer Cd2SnO4; performing radio-frequency sputtering to form the buffering layer Zn2SnO4; performing radio-frequency sputtering to form the n type CdS serving as the window layer; depositing copper-doped CdS at room temperature through physical gas phase method and performing post treatment to form the p type CdS serving as the absorbing layer; or directly growing the p type copper-doped CdS serving as the absorbing layer at a certain temperature through the physical gas phase method; and depositing a metal electrode and connecting a lead. Through the structure and the process, sun light can be better collected and used; p type doping treatment can be effectively performed on the CdS; influences caused by lattice mismatch and interface state are eliminated; and then higher photoelectric conversion efficiency is achieved.

Description

Cadmium sulphide membrane solar cell and preparation method thereof
Technical field
The invention belongs to new energy materials and devices field, particularly a kind of preparation method of semiconductor film solar cell.
Background technology
Cadmium sulfide (CdS) is a kind of important photosensitive semiconductor, is widely used in the optoelectronics field, as photoconductive gas sensor, photoelectric tube, semiconductor laser, Infrared Detectors, solar cell etc.
CdS makes the CdS solar cell exactly in the important application in photovoltaic field, this class solar cell is that basis material prepares with CdS, excellent because of its spectral response and solar spectrum coupling, be fit to do solar cell, can obtain than higher theoretical conversion efficient (see figure 1).The 1950's, the CdS solar battery structure that obtains bigger concern in the photovoltaic field is: the CdS/Cu/ electrode, the common employing of its preparation method is suitably mixed nType CdS monocrystalline plates Cu in one side, and annealing in process, draws contact electrode at last, prepares the CdS solar cell, can obtain 5 ~ 8% photoelectric conversion efficiency.But its production cycle is long, and cost is very high.For this reason, single crystal-like CdS solar cell manufacture craft, developed CdS polycrystal film solar cell again, its structure is: glass/transparent conductive oxide film (TCO)/CdS/Cu/ electrode, can obtain cheap broad area device like this, and the sufficiently high hull cell of efficient there is bigger unit mass power output than the battery made from thicker monocrystal.Its manufacture method is a CdS thin films on the transparent conducting glass, deposits Cu subsequently, and heat treatment then connects lead-in wire at last.Heat treated atmosphere is: N 2Gas or atmosphere like this, might form Cu x S, Cu 2O, therefore, its physical mechanism is too controversial, and what be difficult to judgement and CdS formation is metal-semiconductor junction, or the semiconductor-metal-semiconductor knot, or semiconductor-semiconductor junction, on the other hand, its photoelectric conversion efficiency not high (4 ~ 5%).Recently, and people such as Kashiwaba (see Solar energy materials and solar cells, 2003,75:253-259) structure and the technology to above-mentioned CdS polycrystal film solar cell makes improvements slightly, has obtained reasonable device performance.Structure after they improve is: glass/ITO/Cu/CdS/Al electrode.At first, Cu is deposited on the ITO, at various substrate deposit CdS film, plates electrode at last subsequently, and wherein, Cu is as acceptor impurity.Heat-treat in a vacuum, Cu carries out CdS by diffusion pType mixes, and forms the CdS polycrystal film solar cell of homojunction.Because the thermal diffusion effect forms pThe section bar material is difficult to determine the position of barrier region, adds that CdS has the self compensation effect, is not easy to realize pType mixes, and makes the CdS of preparation be generally nN-type semiconductor N.Therefore, obtain by DIFFUSION TREATMENT pType CdS is difficulty relatively.In addition, under the high temperature, copper also can spread to ITO, electrode performance before the influence, simultaneously, the incomplete diffusion of copper or residually also can influence seeing through of sunlight.
Except above-mentioned CdS base solar cell, also have a kind of CdS base solar cell to adopt " Clevite technology " to be made, be matrix promptly with CdS monocrystalline or film, the Cu of heat of immersion 2Cl 2Solution, reaction generates pType Cu 2S, thus heterojunction CdS solar cell obtained, though this battery cost is lower, the efficient of battery can be accomplished scale production all 5 ~ 8%, this battery is difficult to control pType Compound C u xThe phase of S is easy to generate the mixing phase, and simultaneously, phenomenon falls in battery with declining.
Therefore, above-mentioned two kinds of batteries all do not obtain bigger development.
Summary of the invention
The objective of the invention is further to improve the structure and the preparation technology of CdS base thin film solar battery, propose a kind of with Cd in order to eliminate above-mentioned solar cell deficiency or defective 2SnO 4Be transparency conducting layer, nType CdS is a Window layer, Zn 2SnO 4As the cushioning layer material between transparency conducting layer and the Window layer, pType CdS makes the CdS homojunction solar cell structure of absorbed layer, on this basis, adopts dry process to prepare homojunction CdS solar cell.Adopt said structure and technology, can better collect and utilize sunlight, effectively CdS is carried out pThe type doping treatment, and eliminate the influence that lattice mismatch and interfacial state are brought, thus obtain higher photoelectric conversion efficiency.
For realizing the object of the invention, technical scheme of the present invention is: radio frequency sputtering transparency conducting layer Cd on borosilicate or aluminosilicate glass 2SnO 4, radio frequency sputtering resilient coating Zn subsequently 2SnO 4, next, adopt the radio frequency sputtering method preparation nType CdS adopts physical vapor method room temperature deposition to mix copper CdS and reprocessing as Window layer then, obtains pType CdS makes absorbed layer, perhaps directly growth at a certain temperature of physical vapor method pType is mixed copper CdS and is made absorbed layer, last deposit metal electrodes, and connect lead-in wire.Therefore, the CdS solar cell basic structure of acquisition is: glass/Cd 2SnO 4/ Zn 2SnO 4/ n-CdS/ p-CdS:Cu/ metal electrode.
In such scheme, transparency conducting layer Cd 2SnO 4Thickness 100 ~ 500 nm, resilient coating Zn 2SnO 4Thickness 70 ~ 300 nm, Window layer nThickness 80 ~ 2000 nm of type CdS, absorbed layer pThickness 1000 ~ 9000 nm of type CdS, metal electrode are a kind of in aluminium, silver or the copper, thickness 200 ~ 3000 nm.
In such scheme, the physical vapor method refers to vacuum multi-source coevaporation method or radio frequency sputtering method.
In such scheme, reprocessing comprises original position and ex situ reprocessing, so-called original position reprocessing, refer at room temperature adopt physical vapor method deposition to mix copper CdS after, in vacuum chamber, anneal 250 0C ~ 400 0C is incubated 10 ~ 30 minutes; The ex situ reprocessing refers to the taking-up sample, anneals 250 under nitrogen or inert gas shielding 0C ~ 400 0C is incubated 10 ~ 30 minutes.
In such scheme, growth at a certain temperature refers to that the glass substrate temperature remains on 250 0C ~ 400 0C deposits on the CdS Window layer pType is mixed copper CdS absorbed layer.
In such scheme, pType CdS mixes copper atom percentage concentration 15 ~ 50 at%.
Adopt the CdS solar cell of such scheme preparation, compare, have following advantage and characteristics with two kinds of traditional CdS solar cells:
1. can realize CdS's effectively pType mixes, better controlled doping concentration.And the diffusion method preparation pType CdS, its concentration near electro-conductive glass one side higher, and away from a side concentration fall sharply, can't determine the position of barrier layer.In addition,, cause diffusion not exclusively, influence seeing through of light because the self compensation effect of CdS need deposit a certain amount of copper on electro-conductive glass.
2. adopt above-mentioned homojunction structure, can avoid declines falls, and eliminates the influence that lattice mismatch and interfacial state are brought, thereby obtains higher more stable photoelectric conversion efficiency.
3. technology is simple, easily accomplishes scale production.
Description of drawings
Fig. 1 is the spectral response figure of CdS solar cell.
Fig. 2 is the structural representation of CdS solar cell.
Symbol among Fig. 1: the spectral response curve of 1 expression CdS monocrystalline, the spectral response curve of 2 expression CdS films; Symbolic representation among Fig. 2 is: G is a glass, and F is Cd 2SnO 4, B1 is resilient coating Zn 2SnO 4, W is CdS, and A is CdS:Cu, and B is a metal electrode, for a kind of among Cu, Al or the Ag.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
Referring to accompanying drawing 1, at first, (G) go up deposit transparent conductive layer Cd at Pyrex (as Corning 7059) or aluminosilicate glass (as Corning 1737) 2SnO 4(F) and resilient coating ZnSnO 4(B1), deposit subsequently nType CdS(W) and pType CdS(A), last depositing electrode (B) connects lead-in wire, has so just finished the making of battery.In the CdS thin film solar cell, adopt Cd 2SnO 4(F) do transparent before contact, and be not that common transparent conductive oxide film is (as SnO 2: F, ITO), its reason be the former in the wave band of 800 ~ 1500 nm, serious charge carrier can not occur and absorb, still have ~ 80% transmitance (see J Vac Sci Technol A, 1997,15:1057).Resilient coating Zn 2SnO 4(B1) have the energy gap of broad and higher resistance, little with the cadmium sulfide lattice mismatch, and during the attenuate cadmium sulfide, can prevent the formation of local knot.For the CdS homojunction solar cell, nType CdS(W) deposition adopts sputtering method, because of CdS has the self compensation effect, pType CdS(A) deposition is crucial.The present invention adopts physical vaporous deposition to obtain should pThe type functional layer is mixed copper cadmium sulfide (A), than the method for thermal diffusion, have easy to control, the easy characteristics of preparation. pType CdS:Cu(A) the multi-source coevaporation method is at room temperature used in preparation, perhaps adopts radio frequency sputtering method, and wherein mixing Cu concentration is 15 ~ 50 at%, and the temperature of original position or ex situ reprocessing is 250 0C ~ 400 0C, the time of processing is 10 ~ 30 minutes.If pType CdS:Cu (A) is prepared as under the uniform temperature and grows, i.e. growth in situ, and then the substrate temperature that need add is 250 0C ~ 400 0C.
Embodiment one:
1. on Pyrex (G), the commercial hot-pressure oxidation thing of room temperature radio frequency sputtering target (SnO 2: ~ 33 mol%, CdO: ~ 67%), preparation Cd 2SnO 4(F) conductive layer.Sputtering condition: base vacuum ~ 10 -5Pa, work atmosphere 99.993% pure oxygen, operating air pressure 1 ~ 2 Pa, target and sample distance 6 ~ 9 cm, sputtering power 100 ~ 600 W, sputter thickness 100 ~ 500 nm.After sputter is intact, take out sample, in CdS/Ar atmosphere 580 0C ~ 660 0C heat treatment 10 ~ 30 minutes.
2. room temperature, the commercial hot-pressure oxidation thing of radio frequency sputtering target (SnO on the sample of step 1 2: ~ 33 mol%, ZnO: ~ 67%), preparation Zn 2SnO 4(B1).Sputtering condition: base vacuum ~ 10 -5Pa, work atmosphere 99.993% pure oxygen, operating air pressure 1 ~ 2 Pa, target and sample distance 6 ~ 9 cm, sputtering power 100 ~ 600W, sputter thickness 70 ~ 300 nm.
3. taking out structure is glass (G)/Cd 2SnO 4(F)/Zn 2SnO 4(B1) sample, the commercial CdS target of room temperature radio frequency sputtering is to obtain Window layer cadmium sulfide (W).CdS target purity 99.99% wherein, base vacuum ~ 10 -4Pa, working gas be argon oxygen (oxygen: 1% ~ 2%), operating air pressure 1 ~ 2Pa, target and sample distance 6 ~ 9 cm, sputtering power 30 ~ 100 W, sputter thickness 80 ~ 2000 nm.
4. then, high-purity CdS target is for mixing copper cadmium sulfide target (the wherein atomic percent 15% ~ 50% of copper) in the shift step 3, underlayer temperature is a room temperature, working gas is an argon gas, operating air pressure ~ 1 Pa, target and sample distance 6 ~ 9 cm, sputtering power 20 ~ 300 W, deposition is mixed copper cadmium sulfide (A) 1000 ~ 9000 nm.
5. subsequently, in sputtering chamber to glass (G)/Cd 2SnO 4(F)/Zn 2SnO 4(B1)/and the sample of cadmium sulfide (W)/mix copper cadmium sulfide (A) carries out the original position reprocessing, and pressurize is heated to 250 0C ~ 350 0C, 10 ~ 30 minutes time.
6. last, the taking-up structure is glass (G)/Cd 2SnO 4(F)/Zn 2SnO 4(B1)/and cadmium sulfide (W)/mix the sample of copper cadmium sulfide (A), in vacuum ~ 10 -4Pa, by the grid line mask, electron-beam vapor deposition method deposition 200 ~ 3000 nm aluminium (B1) grid lines, wherein aluminium source purity 99.99% picks out lead-in wire by grid line, and finishing structure is glass (G)/Cd 2SnO 4(F)/Zn 2SnO 4(B1)/cadmium sulfide (W)/the mix cell preparation of copper cadmium sulfide (A)/aluminium (B) grid line.
Embodiment two:
1. on Pyrex (G), the commercial hot-pressure oxidation thing of room temperature radio frequency sputtering target (SnO 2: ~ 33 mol%, CdO: ~ 67%), preparation Cd 2SnO 4(F) conductive layer.Sputtering condition: base vacuum ~ 10 -5Pa, work atmosphere 99.993% pure oxygen, operating air pressure 1 ~ 2 Pa, target and sample distance 6 ~ 9 cm, sputtering power 100 ~ 600 W, sputter thickness 100 ~ 500 nm.After sputter is intact, take out sample, in CdS/Ar atmosphere 580 0C ~ 660 0C heat treatment 10 ~ 30 minutes.
2. room temperature, the commercial hot-pressure oxidation thing of radio frequency sputtering target (SnO on the sample of step 1 2: ~ 33 mol%, ZnO: ~ 67%), preparation Zn 2SnO 4(B1).Sputtering condition: base vacuum ~ 10 -5Pa, work atmosphere 99.993% pure oxygen, operating air pressure 1 ~ 2 Pa, target and sample distance 6 ~ 9 cm, sputtering power 100 ~ 600 W, sputter thickness 70 ~ 300 nm.
3. taking out structure is glass (G)/Cd 2SnO 4(F)/Zn 2SnO 4(B1) sample, the commercial CdS target of room temperature radio frequency sputtering is to obtain Window layer cadmium sulfide (W).CdS target purity 99.99% wherein, base vacuum ~ 10 -4Pa, working gas be argon oxygen (oxygen: 1% ~ 2%), operating air pressure 1 ~ 2Pa, target and sample distance 6 ~ 9 cm, sputtering power 30 ~ 100 W, sputter thickness are 80 ~ 2000 nm.
4. the sample in the step 3 is taken out and put into vacuum chamber, coevaporation high purity copper (99.99%) and CdS (99.99%), underlayer temperature is a room temperature, vacuum degree is ~ 10 -4Pa, deposited copper is 0.02 ~ 0.1 with the ratio of cadmium sulfide speed, mixing copper cadmium sulfide (A) thickness is 1000 ~ 9000 nm.
5. subsequently, in vacuum chamber, sample is carried out the original position reprocessing, temperature 250 0C ~ 400 0C is incubated 10 ~ 30 minutes.
6. last, take out the sample in the step 5, in vacuum ~ 10 -4Pa, by the grid line mask, electron-beam vapor deposition method deposition 200 ~ 3000 nm aluminium (B) grid lines, wherein aluminium source purity 99.99% picks out lead-in wire by grid line, and finishing structure is glass (G)/Cd 2SnO 4(F)/Zn 2SnO 4(B1)/cadmium sulfide (W)/the mix cell preparation of copper cadmium sulfide (A)/aluminium (B) grid line.
Embodiment three:
Original position reprocessing in the step 5 among embodiment one or the embodiment two is changed into the ex situ reprocessing, promptly sample is taken out, under nitrogen or inert gas shielding, heat treatment 250 0C ~ 400 0C, the time is 10 ~ 30 minutes.Other step is identical with embodiment one or embodiment two, can make the cadmium sulfide homojunction solar cell equally.
Embodiment four:
Step 4 among embodiment one or the embodiment two is changed into growth at a certain temperature, and promptly the underlayer temperature among embodiment one or the embodiment two changes 250 into 0C ~ 400 0C, deposition finishes, and takes out sample, puts into electron beam evaporation equipment, vacuum ~ 10 -4Pa, by the grid line mask, electron-beam vapor deposition method deposition 200 ~ 3000 nm aluminium (B) grid lines, wherein aluminium source purity 99.99% picks out lead-in wire by grid line, and finishing structure is glass (G)/Cd 2SnO 4(F)/Zn 2SnO 4(B1)/cadmium sulfide (W)/the mix cell preparation of copper cadmium sulfide (A)/aluminium (B) grid line.
Embodiment five:
In embodiment one to embodiment four, metal electrode (B) changes copper into, adopts the method for sputter or thermal evaporation to prepare copper.Wherein, during thermal evaporation, vacuum ~ 10 -4Pa; During sputter, source purity 99.99%, thickness 200 ~ 3000 nm.Pick out lead-in wire by grid line, finishing structure is glass (G)/Cd 2SnO 4(F)/Zn 2SnO 4(B1)/cadmium sulfide (W)/the mix cell preparation of copper cadmium sulfide (A)/copper (B) grid line.
Embodiment six:
In embodiment one to embodiment four, metal electrode (B) changes silver into, promptly mixes on the copper cadmium sulfide at absorbed layer, adopts the method that applies the silver slurry, the preparation silver electrode, and thickness 200 ~ 3000 nm pick out lead-in wire, and finishing structure is glass (G)/Cd 2SnO 4(F)/Zn 2SnO 4(B1)/cell preparation of cadmium sulfide (W)/mix copper cadmium sulfide (A)/silver (B) does.
Embodiment seven:
Pyrex among the embodiment one to embodiment six are changed into aluminosilicate glass, and other technology does not change.Equally, can make glass (G)/Cd 2SnO 4(F)/Zn 2SnO 4(B1)/cadmium sulfide (W)/the mix battery of copper cadmium sulfide (A)/metal electrode (B).

Claims (9)

1. cadmium sulphide membrane solar cell, structure is: glass/Cd 2SnO 4/ Zn 2SnO 4/ n-CdS/ p-CdS:Cu/ metal electrode is characterized in that: between glass and metal electrode, be followed successively by transparent conductive film Cd 2SnO 4, resilient coating Zn 2SnO 4, Window layer n-CdS, absorbed layer p-CdS:Cu.
2. cadmium sulphide membrane solar cell as claimed in claim 1 is characterized in that: glass is a kind of in Pyrex or the aluminosilicate glass.
3. cadmium sulphide membrane solar cell as claimed in claim 1 is characterized in that: metal electrode is a kind of in aluminium, silver or the copper.
4. a method for preparing as the described cadmium sulphide membrane solar cell of claim 1 to 3 is characterized in that: at radio frequency sputtering transparency conducting layer Cd on glass 2SnO 4, radio frequency sputtering resilient coating Zn subsequently 2SnO 4, next, adopt the radio frequency sputtering method preparation nType CdS adopts physical vapor method room temperature deposition to mix copper CdS and reprocessing as Window layer then, obtains pType CdS makes absorbed layer, perhaps directly growth at a certain temperature of physical vapor method pType is mixed copper CdS and is made absorbed layer, last deposit metal electrodes, and connect lead-in wire.
5. the preparation method of cadmium sulphide membrane solar cell as claimed in claim 4 is characterized in that: transparency conducting layer Cd 2SnO 4Thickness be 100 ~ 500 nm, resilient coating Zn 2SnO 4Thickness be 70 ~ 300 nm, Window layer nThe thickness of type CdS is 80 ~ 2000 nm, absorbed layer pThe thickness of type CdS is 1000 ~ 9000 nm, and the thickness of metal electrode is 200 ~ 3000 nm.
6. the preparation method of cadmium sulphide membrane solar cell as claimed in claim 4 is characterized in that: the physical vapor method refers to vacuum multi-source coevaporation or radio frequency sputtering method.
7. the preparation method of cadmium sulphide membrane solar cell as claimed in claim 4, it is characterized in that: reprocessing comprises original position and ex situ reprocessing, so-called original position reprocessing, refer at room temperature adopt physical vapor method deposition to mix copper CdS after, in vacuum chamber, anneal 250 0C ~ 400 0C is incubated 10 ~ 30 minutes; The ex situ reprocessing refers to the taking-up sample, anneals 250 under nitrogen or inert gas shielding 0C ~ 400 0C is incubated 10 ~ 30 minutes.
8. the preparation method of cadmium sulphide membrane solar cell as claimed in claim 4 is characterized in that: growth at a certain temperature refers to that the glass substrate temperature remains on 250 0C ~ 400 0C.
9. the preparation method of cadmium sulphide membrane solar cell as claimed in claim 4 is characterized in that: the copper atom percentage concentration of mixing copper CdS is 15 ~ 50 at%.
CN2011100844603A 2011-04-06 2011-04-06 Cadmium sulfide thin film solar cell and preparation method thereof Pending CN102185000A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104535084A (en) * 2014-12-30 2015-04-22 上海华虹宏力半导体制造有限公司 Encapsulating method
CN110965025A (en) * 2019-12-20 2020-04-07 平顶山学院 Preparation method of CdS/Si nano film heterojunction

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104535084A (en) * 2014-12-30 2015-04-22 上海华虹宏力半导体制造有限公司 Encapsulating method
CN110965025A (en) * 2019-12-20 2020-04-07 平顶山学院 Preparation method of CdS/Si nano film heterojunction
CN110965025B (en) * 2019-12-20 2021-07-23 平顶山学院 Preparation method of CdS/Si nano film heterojunction

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Application publication date: 20110914